Back to EveryPatent.com
| United States Patent |
5,162,434
|
|
Pielartzik
, et al.
|
November 10, 1992
|
Thermoplastic block copolymers of vinyl or vinylidene polymer segments
and segments of liquid crystalline polymers
Abstract
The thermoplastic block copolymers according to the invention of optionally
substituted vinyl or vinylidene polymer segments and segments of liquid
crystalline polymers are suitable for use as compatibility improvers or
dispersing agents in otherwise incompatible or poorly compatible
thermoplastic polymer mixtures and may be used for the production of
moulded articles, filaments, fibres and films.
| Inventors:
|
Pielartzik; Harald (Krefeld, DE);
Meurer; Kurt P. (Koenigswinter, DE);
Meyer; Rolf-Volker (Krefeld, DE);
Witte, deceased; Joseph W. (late of Cologne, DE);
Witte, heir; by Klaus G. (Berlin, DE)
|
| Assignee:
|
Bayer Aktiengesellschaft (Leverkusen, DE)
|
| Appl. No.:
|
565191 |
| Filed:
|
August 7, 1990 |
Foreign Application Priority Data
| Current U.S. Class: |
525/66; 525/67; 525/68; 525/132; 525/146; 525/184 |
| Intern'l Class: |
C08G 081/02; C08G 063/133; C08G 063/64; C08G 069/44 |
| Field of Search: |
525/132,176,177,68,66,67,146,148,183,184
|
References Cited
U.S. Patent Documents
| 4563508 | Jan., 1986 | Cottis | 525/444.
|
| 4667011 | May., 1987 | Eckhardt | 528/128.
|
| 4798873 | Jan., 1989 | Meurer et al. | 525/333.
|
| 4804711 | Feb., 1989 | Ishihara | 525/146.
|
| 4845158 | Jul., 1989 | Peters | 525/354.
|
| Foreign Patent Documents |
| 0248261 | Dec., 1987 | EP.
| |
| 0253196 | Jan., 1988 | EP.
| |
| 0259868 | Mar., 1988 | EP.
| |
| 1521223 | Mar., 1968 | FR.
| |
Other References
Billmeyer, Textbook of Polymer Science, p. 312, Wiley-Interscience, N.Y.
(1971).
M. Gervais et al., Makromol. Chem., 182:989-995 (1981).
|
Primary Examiner: Short; Patricia
Attorney, Agent or Firm: Connolly and Hutz
Parent Case Text
This application is a continuation of application Ser. No. 309,814, filed
Feb. 13, 1989, now abandoned.
Claims
We claim:
1. Thermoplastic moulding compounds of
A) polypropylene containing carboxyl or carboxylic acid ester anhydride
groups and
B) fully aromatic polyesters, polyester carbonates or polyamides as liquid
crystalline polymers, wherein components A) and B) are polymer blocks
covalently linked by ester or amide groups.
2. Thermoplastic moulding compounds according to claim 1 wherein component
B) is a fully aromatic polyester.
3. Thermoplastic moulding compounds according to claim 1 wherein component
A) is polypropylene and component B) is a fully aromatic polyester
covalently lined by ester groups.
Description
This invention relates to thermoplastic block copolymers of optionally
substituted vinyl or vinylidene polymer segments and segments of liquid
crystalline polymers.
Liquid crystalline homopolymers are known in the art (e.g. A. Cifferi in W.
R. Krigbaum, R. B. Mayer, Polymer Liquid Crystals, Academic Press, 1982:
J. Preston in A. Blumstein. Liquid Crystalline Order in Polymers, Academic
Press, 1978).
Substances are described as "thermotropic" or "liquid crystalline" if they
form liquid crystalline melts. Thermotropic polycondensates are well
known, see e.g.:
F. E. McFarlane et al, Liquide Crystal Polymers II, Contemporary Topics in
Polymer Science. Vol.2, Plenum Publishing Corporation, 1977;
W. J. Jackson and H. F. Kuhfuss, J. Polymer, Polymer Chem. Ed. 14, 2042
(1976);
W. C. Wooten et al in A. Cifferi, "Ultra-high Modules Polymers", Applied
Science Publ,. London 1979, pages 362 et seq;
A. Blumstein et al, "Liquid Crystalline Order in Polymers", Academic Press,
1978:
J. Preston, Angew. Makromol. Chem. 109/110, pages 1-19 (1982);
A. Cifferi, W. R. Krigbaum and R. B. Meyer "Polymer Liquid Crystals",
Academic Press, New York, 1982;
EP 1185, 1340, 8855, 11 640, 15 856, 17 310, 18 145, 18 709, 22 344, 44 205
and 49 615; U.S. Pat. No. 39 91 013, 39 91 014, 40 66 620, 40 67 852, 40
83 829, 41 07 143, 42 26 970, 42 32 143, 42 32 144, 42 45 082, 42 69 965,
43 35 232, 43 81 389, 43 99 270, 43 98 015, 44 47 592 and 45 00 699;
JP 59/1 26 431; and
WO 79/792, 79/1 030 and 79/1 040.
The liquid crystalline state of polymer melts may be investigated with a
polarization microscope. For the investigations carried out, the eyepiece
was equipped with an attachment containing a photoelectric diode at the
focal point of the lens. A measuring amplifier with control device
arranged in series with this attachment was used to adjust the measured
value obtained in the absence of a sample of material when the microscope
was switched on with the Nicol prisms arranged in parallel to 100 scale
divisions. The value obtained when the Nicol prisms were crossed was then
0.01 scale divisions.
Investigation of the polycondensates was carried out after the samples had
been melted at temperatures of from 280.degree. to 400.degree. C. If the
melt between the crossed Nicol prisms was observed to brighten over all or
part of this temperature range, the polycondensate was graded as
thermotropic and liquid crystalline.
The liquid crystalline polycondensates give values of more than 1 scale
division in the measuring arrangement, in most cases values of from 3 to
90 scale divisions. For amorphous melts, on the other hand, such as
aromatic polycarbonates, values of less than 0.1 scale division were
found.
The method described above is particularly suitable for rapid determination
in the laboratory and gives unequivocal results in almost all cases. In
cases of doubt, however, it may be advisable to confirm the presence of
liquid crystalline components in the melt by X-ray wide angle scattering
as described e.g. in "Plastic Crystals, Physico-Chemical Properties and
Methods of Investigation" by G. W. Gray and P. A. Windsor, in particular
Chapter 3, John Wiley and Sons, New York, Sydney, Toronto, 1974.
Blends of vinyl polymers and liquid crystalline polymers prepared by
physical mixing are known from European Patent Specification 00 30 417.
The blends described in the said European Patent Specification are
physical mixtures of the components, as already mentioned, i.e. they have
no covalent bonds between the polyolefines or aromatic polyvinyl compounds
and the segments of the liquid crystalline polymers. It is therefore not
possible to prevent a fundamental incompatibility between these widely
differing polymer components. This manifests itself, for example, in the
unsatisfactory mechanical properties of such mixtures, as our own
experiments have shown.
The present invention relates to thermoplastic moulding compounds of
A) optionally substituted polyolefines or aromatic polyvinyl compounds and
B) liquid crystalline polymers in which components A) and B) are present as
block condensates.
In the thermoplastic moulding compounds according to the invention, the
optionally substituted polyolefine blocks, the aromatic polyvinyl blocks
and the blocks of liquid crystalline polymers are covalently linked by
ester or amide groups. Linking of the blocks with components A) and B) is
carried out by reacting carboxyl-containing, optionally substituted vinyl
polymers having a molecular weight ((Mw) of from 1000 to 350,000,
preferably from 5000 to 200,000, in particular from 10,000 to 100,000,
with the blocks of liquid crystalline polymers or with the monomer units
required for the synthesis of the liquid crystalline polymers under
suitable reaction conditions so that a covalent bond between the vinyl
polymer blocks and the blocks of liquid crystalline polymers will be
formed. The proportion by weight of the polyolefine or aromatic polyvinyl
blocks in this procedure is from 3 to 97% and the proportion by weight of
the blocks of liquid crystalline polymers is from 97 to 3%, based on the
total weight of the blocks. The proportion by weight of the polyolefine or
aromatic polyvinyl blocks is preferably 5 to 70% and that of the blocks of
liquid crystalline polymers form 95 to 30%
The thermoplastic moulding compounds according to the invention are block
polymers of differing structures. They may be build up, for example, of
blocks having the structures AB, ABA, BAB and (AB).sub.x, where x stands
for a number greater than 1, preferably from 2 to 100 (A: vinyl polymer
and vinylidene polymer segments, B: segments of liquid crystalline
polymers).
Vinyl polymers which are used as component A) for the thermoplastic
moulding compounds according to the invention and which are functionalized
by a carboxyl or carboxylic acid anhydride group are known in the art (see
DE-OS 3 618 378).
Aliphatic polyolefines containing carboxyl or carboxylic acid ester
anhydride groups may be prepared by subjecting high molecular weight,
non-functional aliphatic polyolefines to a grafting reaction with
unsaturated carboxylic acids or carboxylic acid anhydrides such as maleic
acid anhydride or by subjecting the high molecular weight, non-functional
polyolefines to an oxidative degradation with air, oxygen or ozone. Thus
according to U.S. Pat. Nos. 3,416,990, 3,437,550 and 3,483,276,
polypropylenes containing carboxylic acid groups may be obtained by
modifying crystalline or amorphous polypropylene with an ethylenically
unsaturated carboxylic acid, a polycarbodylic acid or an unsaturated
carboxylic acid ester.
An example of a crystalline, carboxylated polypropylene polymer which may
be used according to the invention is Hercoprime.RTM. G obtainable by
Hercules, Inc. Bloomington, Del. 19899.
An example of an amorphous carboxylated polypropylene polymer is
Epolene.RTM. E 43 obtainable from Tennessee-Eastman Company, Tennessee.
Another method of obtaining polyolefines containing carboxyl or carboxylic
acid anhydride groups is described in German Offenlegungsschrift 3 618
378. Suitably functionalized polypropylene carboxylic acids and
polypropylene dicarboxylic acids may be obtained by the method described
there.
Aromatic polyvinyl compounds containing carboxyl or carboxylic acid
anhydride groups may be prepared by ionic or radical polymerisation.
Suitable methods are described in the literature and known to the man of
the art: see also Houben-Weyl, Methoden der org. Chemie, Volume 14/1, J.
Thieme Verlag, 1961.
Monofunctional aromatic polyvinyl anions having a narrow molecular weight
distribution are known (see L. J. Fetters, Rubber Chem. Technol, 48,
(1975), page 359).
Bifunctional aromatic polyvinyl anions are also known and are described by
F. Bendermann in Makromol. Chem. 186, (1985), pages 2017-2024 and in U.S.
Pat. No. 1,505,460.
Poly-arylolefine-mono- and di-carboxylic acids, particularly polystyrene
mono- and di-carboxylic acids are generally prepared by anionic
polymerisation followed by carboxylation of the reaction solution (see D.
P. Wyman, V. R. Allen, T. Altares, Jr., J. Polym, Sci.: Parta Vol. 2,
4245-4550 (1964); R. P. Quirk, W.-C. Chen, Macromol. Chem 1982 III, 189
(9), 2071-2076; see also Houben Weyl, Methoden der Org. Chemie, 4th
Edition, Makromolekulare Stoffe I, 761 et seq (1961)).
The vinyl polymers used as component A) generally have a molecular weight
of from 1008 to 350,000, preferably from 2000-800,000, most preferably
from 4000-100,000. The carboxyl group content is about 0.7 to 2.5 carboxyl
groups per molecule, preferably from 1.5 to 2 carboxyl groups per
molecule.
The following optionally substituted vinyl polymers may be used as
component A) according to the invention: Polyolefines such as
polyethylene, polypropylene or polybutylene or aromatic polyvinyl
compounds such as polystyrene, poly-.alpha.-methylstyrene or
polymethylstyrene, preferably polypropylene and polystyrene.
The liquid crystalline polymers used as component B) in the thermoplastic
moulding compounds according to the invention are preferably fully
aromatic polyesters, polycarbonates or polyester amides (see L. L.Chapoy,
Recent Advances in LC-polymers, Elsevier App. Sci. Publ. 1985).
The liquid crystalline polymers may be built up from the following
monomeric units:
a) aromatic hydroxycarboxylic acids,
b) aromatic aminocarboxylic acids,
c) diphenols,
d) aminophenols,
e) aromatic dicarboxylic acids and
f) optionally carbonic acid or derivatives thereof.
Compounds corresponding to the following formulae are examples of suitable
aromatic hydroxycarboxylic acids a):
##STR1##
In the above forumlae,
R.sup.1 to R.sup.4 denote C.sub.1 -C.sub.4 -alkyl (preferably methyl,
ethyl), C.sub.1 -C.sub.4 -alkoxy (preferably methoxy, ethoxy), C.sub.6
-C.sub.10 -aryl or aryloxy (preferably phenyl, phenyloxy, naphthyl,
naphthyloxy, biphenyl, biphenyloxy, tolyl or tolyloxy), C.sub.7 -C.sub.12
-alkylaryl (preferably benzyl), halogen (preferably chlorine or bromine)
or hydrogen, and the valencies enclose an angle of from 45.degree. to
180.degree. between the nucleus and the carboxyl group.
The following are examples of preferred aromatic hydroxycarboxylic acids
(a):
4-Hydroxy-3-methylbenzoic acid, 4-hydroxy-3-phenylbenzoic acid,
4-hydroxy-2-ethylbenzoic acid, 3-chloro-4-hydroxybenzoic acid,
3-bromo-4-hydroxybenzoic acid, 4-hydroxy-3-methoxybenzoic acid,
4-hydroxybenzoic acid, 6-hydroxy-naphthoic acid,
4-hydroxy-3-pheroxybenzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid,
6-hydroxy-5-methyl-2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid,
6-hydroxy-4,7-dichloro-2-naphthoic acid and 2-hydroxybenzoic acid. b
4-Hydroxybenzoic acid and 6-hydroxynaphthoic acid are particularly
preferred.
The following are given as examples of optionally substituted
3-hydroxybenzoic acids (e): 3-Hydroxy-4-methylbenzoic acid,
3-hydroxy-4-phenylbenzoic acid, 3-hydroxy-2-ethylbenzoic acid,
4-chloro-3-hydroxybenzoic acid, 4-bromo-3-hydroxybenzoic acid,
3-hydroxy-4- methoxybenzoic acid, 3-hydroxy-4-phenoxybenzoic acid,
3-hydroxy-2-methoxybenzoic acid and 3-hydroxybenzoic acid.
Unsubstituted hydroxycarboxylic acids such as 3-hydroxybenzoic acid are
particularly preferred aromatic 3-hydroxycarboxylic acids (e).
Compounds corresponding to the following formulae are examples of suitable
aromatic aminocarboxylic acids (b):
##STR2##
In the above formulae, R.sup.1 to R.sup.4 denote C.sub.1 -C.sub.4 -alkyl
(preferably methyl or ethyl), C.sub.1 -C.sub.4 -alkoxy (preferably methoxy
or ethoxy), C.sub.6 -C.sub.10 -aryl or aryloxy (preferably phenyl,
phenyloxy, naphthyl, naphthyloxy, biphenyl, biphenyloxy, tolyl or
tolyloxy), C.sub.7 -C.sub.12 -alkylaryl (preferably benzyl), halogen
(preferably chlorine or bromine) or hydrogen and the valencies enclose an
angle of from 45.degree. to 180.degree. between the nucleus and the
hydroxyl group and between the nucleus and the carboxyl group.
The following are preferred aromatic amino carboxylic acids: 2-Aminobenzoic
acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-chloranthranilic acid,
5-chloranthranilic acid, 3-amino-4-chlorobenzoic acid,
3-amino-4-methylbenzoic acid, 4-amino-3-methylbenzoic acid,
4-amino-3-phenylbenzoic acid, 3-bromo-4-aminobenzoic acid,
4-amino-3-methoxybenzoic acid, 6-aminonaphthoic acid,
4-amino-3-phenylbenzoic acid, 6-amino-5-chloro-2-naphthoic acid,
6-amino-5-methyl-2-naphthoic acid, 6-amino-5-methoxy-2-naphthoic acid and
6-amino-4,7-dichloro.2-naphthoic acid. 4-Aminobenzoic acid and
6-aminonaphthoic acid are particularly preferred. 4-Aminobenzoic acid,
3-aminobenzoic acid and 6-amino-2naphthoic acid are particularly preferred
aromatic amino-carboxylic acids.
The diphenols c) may be compounds corresponding to the following formula
HO--Z--OH (V)
wherein
Z denotes a divalent mononuclear or polynuclear aromatic group containing 6
to 30 carbon atoms and having the two OH groups directly attached each to
a carbon atom of an aromatic system, the two valencies enclosing an angle
of from 45.degree. to 180.degree..
The aromatic groups may be substituted by 1 to 4 C.sub.1 -C.sub.4 -alkyl,
C.sub.1 -C.sub.4 -alkoxy or phenyl, phenoxy, benzyl or halogen groups
(preferably chlorine or bromine) and include not only phenylene,
naphthylene and biphenylene but also phenylene groups connected by oxygen,
sulphur, carbonyl, sulphonyl, C.sub.1 -C.sub.4 -alkylene or alkylidene,
cyclohexylene or hexylidene or --O(CH.sub.2).sub.n O--where n=2 to 4.
The following are examples of preferred diphenols b): Hydroquinone,
4,4'-dihydroxydiphenyl, 4,4,-dihydroxydiphenylether,
4,4'-dihydroxydiphenylethane, 4,4'-dihydroxydiphenoxyethane,
3,5'-dihydroxydiphenyl, 3,5'-dihydroxydiphenylether,
1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene,
1,4-dihydroxynaphthalene, chlorohydroquinone, bromohydroquinone,
methylhydroquinone, phenylhydroquinone, ethylhydroquinone,
2,2'-dimethyl-4,4'-dihydroxydiphenyl, 3,3',
5,5'-tetramethyl-4,4'-dihydroxydiphenyl,
3,5'-dimethoxy4,4'-dihydroxydiphenylether,
1,2-(2-chloro-4-hydroxyphenoxy)ethane, 4-methoxy-2,6-dihydroxynaphthalene,
resorcinol, 3,4'-dihydroxydiphenyl, 3,4'-dihydroxydiphenylether,
3,4'-dihydroxydiphenoxyethane, 1,3-dihydroxynaphthalene,
1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene,
2,7-dihydroxynaphthalene, 4-chlororesorcinol, 4-bromoresorcinol,
4-methylresorcinol, 4-phenylresorcinol, 4-ethoxyresorcinol,
2,5-dichloro-1,6-dihydroxynaphthalene and
4-methoxy-2,7-dihydroxynaphthalene.
Hydroquinone and 4,4'-dihydroxydiphenyl are particularly preferred
diphenols b).
Compounds corresponding to the following formula are suitable aminophenols
d):
HO--Z--NH.sub.2 (VI)
wherein
Z denotes a divalent mononuclear or multinuclear aromatic group containing
6 to 30 carbon atoms and of such a structure that both OH groups are
directly attached each to a carbon atom of an aromatic system, the two
valencies enclosing an angle of 45.degree. to 180.degree..
The aromatic groups may be substituted by 1 to 4 C.sub.1 -C.sub.4 alkyl,
C.sub.1 -C.sub.4 -alkoxy, phenyl, phenoxy, benzyl or halogen groups
(preferably chlorine or bromine) and include not only phenylene,
naphthylene and biphenylene but also phenylene groups connected by oxygen,
sulphur, carbonyl, sulphonyl, C.sub.1 -C.sub.4 -alkylene or alkylidene,
cyclohexylene or hexylidene or --O(CH.sub.2).sub.n O-- where n=2-4.
The following are preferred aminophenols: 3-Aminophenol,
5-amino-2-chlorophenol, 4-aminophenol, 3-amino-2-methylphenol,
3-amino-4-methylphenol, 5-amino-1-naphthol, 6-amino-1-naphthol,
5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-2-naphthol,
6-amino-2-naphthol and 4-amino-1-hydroxybiphenyl.
The aromatic dicarboxylic acids e) may be compounds corresponding to the
following formula
HOOC--A--COOH (VII)
wherein
A denotes a bivalent aromatic group containing 6 to 24 carbon atoms,
preferably 6 to 16 carbon atoms, and the two valencies enclose an angle of
from 45.degree. to 180.degree.. The bivalent aromatic groups may be
substituted by 1 to 4 C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy,
phenyl, phenoxy, benzyl or halogen groups (preferably chlorine or bromine)
and include not only phenylene, naphthylene and biphenylene but also
phenylene groups connected by oxygen, sulphur, carbonyl, sulphonyl,
C.sub.1 -C.sub.4 -alkylene or alkylidene, cyclohexylene or hexylidene or
-O(CH.sub.2).sub.n O- where n=1 to 4.
The following are examples of preferred aromatic groups: 1,4-Phenylene,
1,4-naphthylene and 4,4'-biphenylene in which the two bonds extend
coaxially in opposite directions, 1,5-naphthylene, 1,6-naphthylene and
3,5'-biphenylene in which the two bonds extending in opposite directions
are shifted parallel to one another, and 1,3-phenylene, 1,3-, 1,6-, 1,7-
and 2,7-naphthylene and 3,4'-biphenylene, in which the two bonds are not
localised on adjacent atoms and do not extend in opposite directions with
a coaxial or parallel shift.
The following are examples of preferred aromatic dicarboxylic acids e):
1,4-Naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid.
2,6-naphthalene dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid,
biphenyl-3,3'-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid,
diphenylether-4,4'-dicarboxylic acid, methylterephthalic acid,
methoxyterephthalic acid, chloroterephthalic acid,
4-chloronaphthalene-2,7-dicarboxylic acid, 1,3-naphthalene dicarboxylic
acid, 1,6-naphthalene acid, 1,7-naphthalene dicarboxylic acid,
2,7-naphthalene dicarboxylic acid, biphenyl-3,4'-dicarboxylic acid,
diphenylether-3,4'-dicarboxylic acid, 4-methylisophthalic acid,
5-methylisophthalic acid, diphenylether-4,4'-dichloro-3,3'-dicarboxylic
acid and iso- and terephthalic acid.
Iso- and terephthalic acids are particularly preferred aromatic
dicarboxylic acids e).
The following are mentioned as derivatives for the incorporation of the f)
carbonate groups: Diarylcarbonates such as diphenylcarbonate,
ditolylcarbonate, phenyl-tolylcarbonate and dinaphthylcarbonate,
dialkylcarbonates such as diethylcarbonate, dimethylcarbonate,
dimethyldicarbonate and diethyldicarbonate and glycol carbonate.
Diphenylcarbonate is a preferred derivative for the incorporation of the f)
carbonate groups.
The polyester carbonates according to the invention may contain H, OH,
OC.sub.6 H.sub.5 or groups derived as chain breaking agents as end groups.
Methods for the preparation of liquid crystalline polymers (LCP) are
described in the Patent literature. Liquid crystalline polyesters and
polyester amides are prepared by solvent-free trans-esterification by the
acetate process, conventionally carried out as a single stage or two-stage
process: EP 0 102 719 and 134 204; U.S. Pat. No. 520,043 and 468,240, and
EP 63 880 and 67 032. LC polyesters and polyester carbonates may also be
prepared by solvent-free transesterification by the phenyl ester process:
U.S. Pat. No. 4,371,600 and 4,435,561. EP 0 015 856 and 132 637 and DE 2
704 315.
The thermoplastic block copolymers according to the invention are condensed
in the form of blocks, as already mentioned above, by the reaction of
optionally substituted vinyl polymers containing carboxyl groups or
carboxylic acid anhydride groups with the liquid crystalline polymers.
Instead of using liquid crystalline polymers, the corresponding
functionalised vinyl polymers may be condensed with the monomeric units of
the liquid crystalline polymers. The condensation reaction links the
polyolefine segments with the segments of liquid crystalline polymers by
way of phenolic OH groups as esters or by way of NH groups as amide
groups.
Linkage of the blocks A and B by ester or amide groups is carried out by
condensation processes in which polyvinyl-LC-polyester and
polyvinyl-LC-polyester amide block copolymers are preferably prepared by
the solvent-free acetate esterification process, either from the monomer
units or from previously prepared oligomers.
Polyvinyl-LC-polyester carbonate and polyvinyl-LC-polyester block
cocondensates are prepared by solvent-free trans-esterification by the
diphenylcarbonate process from suitable monomer units by way of the phenyl
esters which are formed in situ or they are prepared from preformed phenyl
esters.
Previously prepared oligo ester or oligo ester carbonate segments may also
be used.
Furthermore, the solvent-free trans-esterification of high molecular weight
LC-polymers with suitable polyvinyl segments may be carried out in an
extruder.
Condensation of the blocks A with blocks B may be carried out at
temperatures from 100.degree. to 350.degree. C., preferably at 200.degree.
to 330.degree. C.
Conventional catalysts for the preparation of polycondensates (see e.g. EPO
0 132 637) may be added in quantities of from 0.0005 to 5%, based on the
total quantity of starting components.
The thermoplastic moulding compounds according to the invention may form
anisotropic melts when heated. This may have an advantageous effect on
their use, e.g. when they are mixed with other polymers. The thermoplastic
moulding compounds according to the invention vary in their spectra of
properties according to the block length and block content. Thus block
cocondensates according to the invention having a great vinyl polymer
block length (corresponding to a high molecular weight) and containing a
high proportion of vinyl polymer sequences have properties resembling
those of vinyl polymers, and the fluidity, notched impact strength and
dimensional stability under heat is increased by the incorporation of
about 3 to 30% of blocks of liquid crystalline polymers. A particularly
marked structural viscosity characterises thermoplastic moulding compounds
according to the invention which contain about 30 to 60% of polyolefine
blocks and about 40 to 70% of blocks of liquid crystalline polymers.
The thermoplastic moulding compounds according to the invention may be used
as compatibility improvers or dispersing agent in otherwise incompatible
or poorly compatible thermoplastic polymer mixtures such as
polypropylene/LCP blends.
The action of the thermoplastic moulding compounds according to the
invention as polymer dispersers is also evident when polypropylene/LCP
blends are observed under an optical light microscope. These blends show
an irregular distribution composed of units of varying sizes when used
without polymer dispersers but the phases are found to become uniform and
reduced in size when about 10% of the thermoplastic moulding compounds
according to the invention are added.
The thermoplastic moulding compounds according to the invention containing
about 97 to 70% of blocks of liquid crystalline polymers are found to have
a particularly high capacity for recrystallisation when processed from the
melt. The fluidity of the products is satisfactory so that the products
are also capable of filling complex moulds.
The thermoplastic moulding compounds according to the invention may also be
used for the manufacture of
electrotechnical articles such as insulators, printed circurts,
plug-and-socket connections, parts of fittings, and coverings of
integrated circuits,
parts of industrial chemical apparatus such as pipes, container linings,
rotors, sliding bearings or seals.
parts for the internal fittings of aircraft and
parts of medical technical apparatus, air conditioning plants and valves.
The thermoplastic moulding compounds according to the invention may also be
used as covering or coating materials (pulverulent or dispersed). They are
also suitable for the preparation of reinforced or filled moulding
compounds containing about 5 to 75% by weight of reinforcing agents or
fillers, based on the reinforced or filled moulding compounds.
The invention further relates to the use of the new thermoplastic moulding
compounds for the production of moulded articles, filaments, fibres and
films.
Preparation of the poly-.alpha.-alkyl-olefine blocks
Preparation of the polypropylene (PP) carboxylic acids (according to German
Offenlegungsschrift 36 18 378)
6000 g/h of isotactic polypropylene having an average molecular weight of
340,000 are introduced into an extruder (ZSK 32) having a length/diameter
ratio of LD=40, heated to 250 .degree. to 260.degree. C. and mixed with
1500 Nl/h of air under pressure (Nl/h=normal litres per hour).
Downstream of the zone of introduction of air, the cylinder temperature of
the extruder is maintained at 210.degree. C. The excess air leaves in the
degasification zone and the degraded polypropylene is spun off at the
nozzle. Carboxy-functionalised polypropylene having a molecular weight of
about 70,000 and a functionality of about 2 is obtained. The acid number
is therefore above 1.5 mg KOH/g substance.
Preparation of the PP-carboxylic acid phenyl ester
600 g of Diphenylcarbonate, 420 g of a carboxy functionalised polypropylene
(Mw 70,000: acid number about 1.5) and 2.6 g of imidazole are stirred at
180.degree. C. until evolution of CO.sub.2 ceases. The reaction
temperature is raised to 250.degree. C. for 30 minutes. After the melt has
cooled to 160.degree. C., the phenyl ester is precipitated by introduction
into 4 l of methanol. suction filtered, washed free from phenol and dried.
______________________________________
General method of experimental procedure for the preparation
of carboxymonofunctional polystyrene carboxylic acids
______________________________________
Example of a formulation (Molecular weight = 2000)
Autoclave 40 l; N.sub.2 ; RT
Cyclohexane [ml] 18000 (H.sub.2 O content < 2 ppm)
Styrene [ml/g/mol]
1584/1440/13.8
THF (ml] 1500 (H.sub.2 O content < 2 ppm)
Temp. [.degree.C.]
0
Buli [ml/mmol] 276.8/692 (diluted with
500 ml of cyclohexane)
Reaction time
[h] 2
CO.sub.2 [bar] 10 (autoclave)
Reaction time
[min] 15
with CO.sub.2
CH.sub.3 COOH/H.sub.2 O
[ml/ml] 500/1000
______________________________________
Example of a formulation (Molecular weight = 5000)
Autoclave 40 l; N.sub.2 ; RT
Cyclohexane [ml] 18000 (H.sub.2 O content < 2 ppm)
Styrene [ml/g/mol]
1584/1440/13.8
THF [ml] 1500 (H.sub.2 O content < 2 ppm)
Temp. [.degree.C.]
0
Buli [ml/mmol] 115.2/288
Reaction time
[h] 2
CO.sub.2 [bar] 10 (autoclave)
Reaction time
[min] 15
with CO.sub.2
CH.sub.3 COOH/H.sub.2 O
[ml/ml] 240/500
______________________________________
Example of formulation (molecular weight = 10,000)
Autoclave 40 l: N.sub.2 ; RT
Cyclohexane [ml] 18000 (H.sub.2 O content < 2 ppm)
Styrene [ml/g/mol]
1584/1440/13.8
THF [ml] 1500 (H.sub.2 O content < 2 ppm)
Temp. [.degree.C.]
0
Buli [ml/mmol] 57.6/144
Reaction time
[h] 2
CO.sub.2 bar 10 (autoclave)
Reaction time
[min] 15
with CO.sub.2
CH.sub.3 COOH/H.sub.2 O
[ml/ml] 120/500
______________________________________
General experimental procedure for the preparation of
carboxydifunctional polystyryl carboxylic acid
______________________________________
Example of a formulation (bifunctional) Molecular weight =
14000)
Flask 0.5 l: N.sub.2 ; RT
THF [ml] 300
.alpha.-methylstyrene
[ml/g/mol]
60/54.8/0.463
Temp. [.degree.C.]
-40
Na naphthenate
[ml/mmol] 17.4
Reaction time
[h] 1
Introduction of CO.sub.2
[min] 10
Reaction time
[min] 30
with CO.sub.2
0.2N HCl [ml] 100
______________________________________
EXAMPLE 1
Preparation of polypropylene/liquid crystalline (LG) polyester block
copolymers
The substances summarized in Table 1 and 0.1 g of magnesium acetate
(anhydrous) and 0.15 g of antimony trioxide were weighed into a 1 l ground
glass vessel equipped with ground glass cover, stirrer, nitrogen inlet and
distillation attachment connected to a condenser.
The reaction mixture was heated to 170.degree. C. in a salt bath under a
nitrogen atmosphere. As soon as the distillation of acetic acid slowed
down (after about 45 minutes), the temperature in the reaction vessel was
raised to 250.degree. C. in the course of one hour and to 330.degree. C.
in the course of a further hour. After distillation had terminated, the
pressure was lowered to about 1 mbar in the course of 30 minutes.
The viscosity of the resulting polymer melt rose sharply during this vacuum
phase. The melt was therefore stirred more slowly. At the end of this
phase, the total quantity of acetic acid (containing the remainder of
acetic anhydride) had been collected.
The light brown products obtained were ground and subjected to a solid
phase after-condensation at 250.degree. C. (under a vacuum of about 1
mbar/24 hours. An optically anisotropic melt phase was observed in the
region of from 250.degree. to 350.degree. C.
TABLE 1
______________________________________
1a) 296.30 g of p-hydroxybenzoic acid
109.0 g of hydroquinone
30.7 g of 4,4'-dihydroxydiphenyl
191.40 g of isophthalic acid
454.80 g of acetic anhydride
60.86 g of carboxylated polypropylene, molecular
weight 70,000, acid number 1.5
1b) 296.30 g of p-hydroxybenzoic acid
109.00 g of hydroquinone
30.7 g of 4,4'-dihydroxydiphenyl
190.8 g of isophthalic acid
454.8 g of acetic anhydride
136.90 g of carboxylated polypropylene, molecular
weight 70,000, acid number 1.5
1c) 296.30 g of p-hydroxybenzoic acid
109.0 g of hydroquinone
30.7 g of 4,4'-dihydroxydiphenyl
190.04 g of isophthalic acid
234.70 g of carboxylated polypropylene, molecular
weight 70,000, acid number 1.5
454.8 g of acetic anhydride
______________________________________
EXAMPLE 2
Method of preparation of polypropylene/LC-polyester amide block copolymers
The substances summarized in Table 2 and 0.1 g of magnesium acetate
(anhydrous) and 0.15 g of antimony trioxide were weighed into a 1 l ground
glass vessel equipped with ground glass cover, stirrer, nitrogen inlet and
a distillation attachment connected to a condenser.
The reaction mixture was heated to 170.degree. C. in a salt bath under a
nitrogen atmosphere. As soon as the distillation of acetic acid slowed
down (after about 45 minutes), the temperature in the reaction vessel was
raised to 250.degree. C. in the course of one hour and to 330.degree. C.
in the course of a further hour. After distillation had terminated, the
pressure was lowered to about 1 mbar in the course of 30 minutes.
The viscosity of the resulting polymer melt rose sharply during this vacuum
phase. The melt was therefore stirred more slowly. The total quantity of
acetic acid (containing the remainder of acetic anhydride) had been
collected by the end of this phase.
The light brown products obtained were ground and subjected to a solid
phase after-condensation at 250.degree. C. (at a vacuum of about 1 mbar/24
hours). An optically anisotropic melt phase was observed in the region of
from 250.degree. to 350.degree. C.
TABLE 2
______________________________________
2a) 273.47 g of p-hydroxybenzoic acid
22.63 g of p-aminobenzoic acid
109.00 g of hydroquinone
30.70 g of 4,4'-dihydroxybiphenyl
191.40 g of isophthalic acid
454.80 g of acetic anhydride
60.8 g of carboxylated polypropylene, molecular
weight 70,000, acid number 1.5
2b) 273.47 g of p-hydroxybenzoic acid
22.63 g of p-aminobenzoic acid
109.00 g of hydroquinone
30.70 g of 4,4'-dihydroxybiphenyl
191.40 g of isophthalic acid
454.80 g of acetic anhydride
136.9 g of carboxylated polypropylene, molecular
weight 70,000, acid number 1.5
2c) 273.47 g of p-hydroxybenzoic acid
22.63 g of p-aminobenzoic acid
109.00 g of hydroquinone
30.70 g of 4,4'.dihydroxybiphenyl
191.40 g of isophthalic acid
454.80 g of acetic anhydride
234.7 g of carboxylated polypropylene, molecular
weight 70,000, acid number 1.5
______________________________________
EXAMPLE 3
Method of preparation of polypropylene/LC-polyester carbonate block
copolymers
The substances summarized in Table 3 and 1.5 g of imidazole were weighed
into a reaction vessel equipped with stirrer, column and distillation
bridge.
The liberation of CO.sub.2 began at a reaction temperature of 160.degree.
C. The reaction temperature was raised to 180.degree. C. in the course of
15 minutes, kept constant for 60 minutes, raised to 220.degree. C. and
then kept constant until the evolution of CO.sub.2 ceased.
The reaction mixture was heated to 250.degree. C. and the pressure in the
reactor was lowered stepwise to 30 mbar. After one hour, distillation had
slowed down to such an extent that the reaction temperature could be
raised to 275.degree. C. and subsequently to 300.degree. C. when the
liberation of phenol had been substantially completed, the pressure in the
reactor was reduced to 0.2 mbar. The reaction was completed after one hour
under these condensation conditions.
The light brown products obtained were ground and subjected to a solid
phase condensation at 250.degree. C. (at a vacuum of 1 mbar/24 hours). An
optically anisotropic melt phase was observed in the region of from
250.degree. to 250.degree. C.
TABLE 3
______________________________________
3a) 305.00 g of hydroxybenzoic acid
112.60 g of hydroquinone
31.60 g of 4,4'-dihydroxybiphenyl
28.20 g of isophthalic acid
779.60 g of diphenylcarbonate
52.03 g of the phenyl ester of polypropylene carboxylic
acid
1.5 g of imidazole
3b) 112.94 g of hydroquinone
117.07 g of the phenyl ester of polypropylene carboxylic
acid
305.00 g of hydroxybenzoic acid
31.60 g of 4,4'-dihydroxybiphenyl
28.20 g of isophthalic acid
779.60 g of diphenylcarbonate
1.5 g of imidazole
3c) 113.38 g of hydroquinone
200.68 g of the phenyl ester of polypropylene carboxylic
acid
305.00 g of hydroxybenzoic acid
31.60 g of 4,4'-dihydroxybiphenyl
28.20 g of isophthalic acid
779.60 g of diphenylcarbonate
1.5 g of imidazole
3d) 114.81 g of hydroquinone
468.24 g of the phenyl ester of polypropylene carboxylic
acid
305.00 g of hydroxybenzoic acid
31.60 g of 4,4'-dihydroxybiphenyl
28.20 g of isophthalic acid
779.60 g of diphenylcarbonate
1.5 g of imidazole
3e) 118.14 g of hydroquinone
1092.50 g
of the phenyl ester of polypropylene carboxylic
acid
305.00 g of hydroxybenzoic acid
31.60 g of 4,4'-dihydroxybiphenyl
28.20 g of isophthalic acid
779.60 g of diphenylcarbonate
1.5 g of imidazole
______________________________________
EXAMPLE 4
Method of preparation of PP/LC-polyester carbonate block polymers by
solvent-free transesterification in an extruder
4.0 kg of a LC-polyester carbonate corresponding to the basic composition
from Example 3b) and 1.0 kg of the phenyl ester of polypropylene
carboxylic acid are compounded at 330.degree. C. in a ZSK 32 (double shaft
extruder with evaporator dome).
The product is drawn off as a strand, cooled in a water bath (1 to 3 m) and
granulated.
Polypropylene and the phenyl esters of carboxylated polypropylenes are
readily soluble in apolar solvents such as hot toluene or xylene, in
contrast to the LC polymers. To examine the chemical coupling of these
incompatible blocks with each other, the products were finely ground and
extracted with hot xylene for 48 hours to remove PP blocks which had not
been chemically coupled. Only small quantities (about 0.5%) of
polypropylene which had not been carboxylated could be extracted as
by-product from the carboxylation products.
The degree of coupling of the PP blocks was greater than 99% in all cases.
Some important thermal properties of selected products are summarized in
Table 5.
EXAMPLE 5
(Comparison Example)
4 g of a polyester carbonate corresponding to the basic composition from
Example 3b) and 1 kg of commercial polypropylene are compounded as in
Example 4 in a ZSK 32 (double shaft extruder with evaporate dome).
The product is drawn off in the form of a strand, cooled in a water bath
and granulated.
EXAMPLE 6
Preparation of polystyrene/LC polyester carbonate block cocondensates
The raw materials summarized in Table 4 are reacted in accordance with the
instructions given in Example 3.
TABLE 4
______________________________________
6a) 314.00 g of p-hydroxybenzoic acid
716.55 g of hydroquinone
32.60 g of 4,4'-dihydroxydiphenyl
29.05 g of isophthalic acid
788.6 g of diphenyl carbonate
14.9 g of polystyrene carboxylic acid (molecular
weight = 5000)
6b) 314.00 g of p-hydroxybenzoic acid
126.40 g of hydroquinone
32.60 g of 4,4'-dihydroxydiphenyl
190.8 g of isophthalic acid
807.45 g of diphenylcarbonate
14.9 g of polystyrene dicarboxylic acid (molecular
weight 1000)
6c) 314.00 g of p-hydroxybenzoic acid
116.55 g of hydroquinone
32:60 g of 4,4'-dihydroxydiphenyl
29.05 g of isophthalic acid
788.6 g of diphenylcarbonate
14.9 g of polystyrene dicarboxylic acid (molecular
weight = 10,000)
______________________________________
Polystyrene and the phenyl esters of the carboxylated polystyrenes are
readily soluble in hot xylene, in contrast to the LC polymers.
To test for chemical coupling, the PS/LC block cocondensates were finely
ground and extracted with hot xylene for 48 hours to dissolve out any
polystyrene blocks which were not chemically bound. Only small proportions
(about 0.3 to 0.5%) of polystyrene which had not been carboxylated and had
been present as by-product in the starting materials could be extracted.
TABLE 5
______________________________________
Product Tg (.degree.C.)
.DELTA.HU (J/g)
Tu (.degree.C.)
______________________________________
PP/LC polyester
block cocondensates
1a 121 6.1/4.3 148.9/287.5
1b 123 10.7/4.0 148.2/289.3
1c 119 35/3.8 149.4/287.8
PP/LC polyester
amide block cocondensates
2a 129 6.2/4.6 149.1/304.6
2b 128 11.7/4.3 147.1/305.1
2c 131 34.3/4.5 150.0/302.1
PP/LC polyester carbonate
block cocondensates
3a 93 10.1/8.9 148.3/225.8
3b 90 18.4/10.3
148.6/225.7
3c 95 37.1/9.8 149.1/224.9
______________________________________
The phase conversion of the polypropylene blocks takes place in the
temperature range of from 140.degree. to 150.degree. C.; that of the LC
blocks is found to occur at higher temperatures:
______________________________________
LC-polyester 288.degree. C.
LC-polyester amide 304.degree. C.
LC-polyester carbonate
225.degree. C.
______________________________________
The mechanical properties of some selected products are summarized in Table
6. It is noticeable that at high LC block contents, the properties of the
LC phase dominate. At PP block contents of upwards of about 20-30%, the
properties gradually change in the direction of those of pure
polypropylene.
TABLE 6
______________________________________
Product
a.sub.n /a.sub.k
R E.sub.Z
B E.sub.B
HDT-A
______________________________________
1b 24/20 104 12,700 110 7.800 125
2b 33/18 130 11,200 175 10,300 138
3a 43/35 136 11,700 110 8,200 148
3b 44/30 147 10,600 102 7,500 142
3c 25/20 100 6,400 75 3,220 125
4 35/30 140 10,000 100 7,600 138
5 4/4 35 2,000 22 2,530 90
______________________________________
a.sub.n /a.sub.k : Impact strength and notched impact strength
(kJ/m.sup.2)
R: Tear resistance (MPa)
E.sub.Z : TensionE modulus (MPa)
B: Flexural strength (MPa)
E.sub.B : FlexuralE-modulus (MPa)
Top